Insecticides



Patented Oct. 31, 1950 UNITED STATES PATENT OFFICE INSECTICIDES Walter D. Harris, Naugatuck, and Theodore W. Kerr, Seymour, Conn., assignors to United States Rubber Company, New York, N. Y., a.

- corporation of New Jersey No Drawing. Application April 25, 1946, Serial No. 664,988

17 Claims. 1

1,1,1-trichloroethane (DDT). The mixed aliphatic-aromatic acetals of chloral may be represented by the general formula in which X- is an aliphatic radical and Y is an aromatic radical. Examples of the aliphatic radicals X are alkyd, cycloalkyl, haloalkyl, cyanoalkyl, alkoxyalliyh.hydroxyalkyl. Examples of the alkyl ether linkage (e. g. haloalkyl, cyanoalkyl, alkoxyalkyl or hydroxyalkyl ether linkage) and applied loci to be protected against insects in undiluted form, or as dusts when admixed with or adsorbed on powdered solid inert carriers, such as clay or talc, or as liquids or sprays when in a liquid carrier, as in solution in a suitable solvent, or dispersed in a suitable non-solvent medium, for example, water. including plant parts) which are subject to attack by insects, the mixed aliphatic-aromatic acetals of chloral of the present invention are preferably applied as aqueous emulsions containing a dispersing agent. The chemicals may be used admixed with 'carriers that are active of themselves, for example, other insecticides, fungicides or bactericides.

Detailed procedures for the preparation of various compounds of the present invention are the aryloxy group may be considered a hydrocarbon aryl (e. g. phenyl or naphthyl) ether linkage,

or a substituted aryl'ether linkage (e. g. haloaryl,

nitroaryl, alkaryl; or alkoxyaryl ether linkage).

The compounds of the present invention are readily prepared by refluxing the selected phenolic compound with the selected a,fi, B,p-tetrachloroethyl aliphatic ether. The ,fl,,3, 8-tetrachloroethyl aliphatic ethers are known and described in the literature. phenol and the chloroether proceeds smoothly and The reaction between the described in Examples I to XVII given below.

' EXAMPLE I 5 I -ethOaiy-I-phenoa:y-2,2,2-trichloroethane A solution of 100 g. of phenol and 19 g. of symtetrachloroethyl ethyl ether was refluxed at aromaticyradicalsyaare phenyly naphthyl' ha1o a atmospheric pressure for two hours. The dark phenyl, nitrophenyl, alkylphenyl, alkoxyphenyL colored reaction product was poured into 1500 cc. The chemicals of the invention may also be classed of we water- The mlxturewas slurred for a few as l-alkoxy-l-aryloxy 2,2,2 trichloroethanes, m then w made by addmg an excess where the alkoxy group may be considered a o aqueous Sodmm hydroxldeh 011 layer I hydrocarbon alkyl ether linkage or a Substituted g separated and the water layer was extracted with 300 cc. of ether. The ether extract was added to the oil and the combined solution was washed with water. The ether solution was dried over calcium chloride, concentrated on the steam bath and finally distilled under reduced pressure. The fraction boiling at 130-131 C./4 mm. was a clear, light yellow, almost odorless liquid. Analysis calculated for C1oH11O2C13: 39.46% Cl; found 39.25% Cl.

The equation for the reaction is:

octane/100.1 1. HOG

in good yields. No catalyst is necessary. In general, it is advisable to use an excess of the lower 001:0 EC! boiling component, that the temperature may be controlled more readily. The mixture is refluxed, preferably under reduced pressure, from EXAMPLE 11 one to five hours. The reaction mixture can then be fractionated without washing, or if extreme Lemon/'1'(z'g'dwhlomphenow)'222' purity is desired, unreacted phenol can be retrwhlomethane moved by washing with dilute aqueous alkali be- A solution of 20 g. of 2,4-dichlorophenol in 40 g. fore distilling. Most of these materials are colorof a,p, 3,fl-tetrachloroethyl ethyl ether was heated less. almost odorless liquids. under reflux for three hours. The temperature The chemicals of the present invention may be climbed gradually to about 216 C. Hydrogen In protecting plants (the term chloride was evolved rapidly during the first part of the reaction period. The oil layer was washed with dilute aqueous sodium hydroxide, then with water. Finally, it was distilled under reduced pressure. A yield of 29 g. (70% of theoretical) of water-white oil boiling at 134-l38 C./2 mm. was obtained. Analysis calculated for CmHsOaCls: 52.38% Cl; found 51.72% Cl.

EXAMPLE III I -ethoa:y-1 (2,4,6-trichlorophenoxy) 2,2,2-trichloroethane This compound was prepared by reacting 2,4,6- trichlorophenol with (1,153.86 tetrachloroethyl ethyl ether according to the method of Example 11. Boiling point 145-150 C./l mm.

EXAMPLE IV 1 -p-chloroethoa:y-1 2,4-dichlorophenomy) 2,2,2 -trichloroethane This compound was prepared by reacting 2,4- dichlorophenol with a,fi,;8,fi-tetrachloroethyl fichloroethyl ether according to the method of Example II. Boiling point PTO-172 C./2 mm. Refractive index, 12 1.5580. Analysis calculated for CioHaO2Clat 57.05% Cl; found 56.41% Cl.

EXAMPLE V 1 -ethoa:y-1 -(p-chlorophenacy) 2,2,2-trichloroethane A solution of '70 g. of afififi-tetrachloroethyl ethyl ether and 25.7 g. of p-chlorophenol was refluxed at atmospheric pressure for about 1 hours. During this time hydrogen chloride was evolved rapidly and the solution took on a reddish brown color. Refluxing was continued under reduced pressure (about 100 mm.) for two hours. In this way the temperature of the reaction mixture was maintained near 150 C. No further darkening was noted during this period. The reaction mixture was washed with dilute aqueous alkali to remove the unchanged p-chlorophenol, then with water. The oil layer was separated and fractioned under reduced pressure. A. fore-run consisting mostly of unreacted tetrachloroethyl ether weighed 20 g. The main fraction boiled at 120-122 C./1.l mm. A yield of 60.8 g. (87% of theoretical) of almost water-white oil was obtained. It had a slight not unpleasant odor. Analysis calculated for C1oHioO2C14: 46.65% Cl; found 46.28% Cl.

EXAMPLE VI 1 -etho.1:y-1 (2,4,5-trichlorophenoscy) 2,2,2-trz'chloroethane This compound was prepared by reacting a,fi,;8,;9-tetrachloroethyl ethyl ether with 2,4,5- trichlorophenol according to the method of Example V. Boiling point 157 C./1.5 mm. Refractive index, n 1.5557. Analysis calculated for C10H802C16I 57.05% Cl; found 56.5% C1.

EXAMPLE VII 1 -p-chloroethoxy-1 -pheno:z:y- 2,2,2-trichloroethane This compound was prepared by reacting a,c,;3,;8-tetrachloroethy1 fl-chloroethyl ether with phenol, according to the method of Example V. Boiling point 129 C./ 1.7 mm. Refractive index,

12,, 1.5397. Analysis calculated for Ciel-11002014: 46.65% Cl; found 46.14% C1.

EXAMPLE VIII 1 -5-chloroethozy-1 Z-naphthoxy) 2,2,2-trichloroethane This compound was prepared by reacting 1. 6pm-tetrachloroethyl c-chloroethyl ether with 2-naphthol, according to the method of Example V. Boiling point VIZ-190 C./0.3 mm.

EXAMPLE IX 1 -fi-chloroethoary-1-(p-chlorophenozcy) 2,2,2-trichloroethane This compound was prepared by reacting a,fi,{3,l3tCtlflChlOlOEthYl B-chloroethyl ether with p-chlorophenol, according to the method of Example V. Boiling point 157 C./2 mm. Refractive index, n 1.5488. Analysis calculated for Ciel-1902015: 52.38% Cl; found 51.99% Cl.

EXAMPLE X 1 -ethoa:y-1- (o-chlorophenoxy) 2,2,2-trichloroethane EXAMPLE XI 1 -etho.'z:y-1 (m-chlorophenoxy) 2,2,2-trichloroethane This compound was prepared by reacting mchlorophenol with 8, 3,;3-tetrachloroethyl ethyl ether according to the method of Example X. Boiling point 136-137 C./2 mm. Analysis calcu lated for C1oHicO2Cl4Z 46.65% C1; found 46.68% C1.

EXAMCPLE XII 1 -etho:ny-1 (p-m'trophenoxy) 2,2,2-trichloroethane This compound was prepared by reacting pnitrophenol with a,p,p,c-tetrachloroethyl ethyl ether according to the method of Example X. The compound was a light yellow solid having a melting point of 67-69 C. Analysis calculated for C10H10O4NC13: 33.82% C1; found 32.28% Cl.

EXAMPLE XIII 1 -ethoa:z/-1 (p-methylphenoscy) -2,2,2-

trichloroethane This compound was prepared by reacting pmethylphenol with a,cflfi-tetrachloroethyl ethyl ether according to the method of Example X. Boiling point C./O.7 mm.

EXAMPLE XIV 1-ethoa:y-1-(p-ethoxyphenoxy) -2,2,2-

trichloroethane This compound was prepared by reacting pethox phenol with a.fl,/3,B-tetrachloroethy1 ethyl ether, according to the method of Example X. Boiling point Hill- C/1.2 mm. Refractive index, n 1.5216.

EXAMPLE XV organisms under test. The bean leaves were then infested with approximately 40 Mexican 1 'chlorophenoxy bean beetles (Epilachna varivestis) in four reptrzchloroethane This compound was prepared by reacting pchlorophenol with a,fi,p,,s-tetrachloroethyl butyl ether, according to the method of Example X. Boiling point 130-140 C./0.4 mm. Analysis calculated for C12H14O2Cl4: 42.71% Cl; found 41.97% Cl.

EXAMPLE XVI licates of each treatment. The bean leaves were placed in separate covered petri dishes. After 48 hours observations disclosed mortalities of the beetles on the leaves treated with the various mixed aliphatic-aromatic acetals' of chloral, as shown in the following table. In untreated leaves ther was no mortality of the beetles.

- Per Cent l-hexoxy-i (p-chlorophenoxy) -2,2,2- 011mm] Mortality trichloroethane T... d d b u w i-as -rea rrarmi--t. 138

s compoun was prepare y reac ng pr-m o n e yc owe me.

l-Etho -l-(o-chloro henox )-2,2,2-trichloroethane. 100.0 Chlorophenol with filflfi y hexyl l-Ethog-l-(m-chlorgpheno y)-2 2,2-trlchloroethane. 100.0 ether, according to the method of Example X. igg-l gz i d cili r g enox zfiz tr cggirogt tg e. 100.0 Boiling point 140-150 c./0.4 mm. Analysis 'calwas. fl 100.0 culated for C14H1aO2Cl4; 39.39% Cl; found 20 fiQgg i p w y)- c 87 5 C1. l-Ethoxy-1- p-nitrophenoxy)-2,2,2-trichloroethane 85:0 l-Butoxy-l-p-ehlorophenoxy)-2,2,2-trichloroethane.. 100.0 WLE XVII l-Hexoxy-l-(p-chlorophenoxy)-2,2,2-trichloroethane 82.5 l-Octoxy-lp-chloro henoxy)-2,2,2-trichloroethane 55.0 1 -OCtO-'B!l-1 -(p-Chl0TOphen0x1/) -2,2,2- l-fichloroet oxy-l-p enoxy-2 2,2-trichloroethane 100.0 trichloroethane l-gl-chhtir oethoxy-l-(p-c orophenoxy) --2,2,2-tri- 100 0 c oro m d b ti l-fih-lchlotrlfiflhoxy-l-(2,4-dichlorophenoxy)-2,2,-tri- 100 0 This compound was prepare y reac ng pc Owe e l h l chlorophenol with a,p,,s,,e-tetrachloroethyl octyl 1 ,,h...' My 1 (2 naphthoxy) mch 5&0 th r according t th th d f Ex l X l-Ethoxy-l-(p-methylphenoxy)-2,2,2-trichloroethane 100.0

. LE 11 th h -2 2,24: h h 100. Boiling point l55165 C./0.4 mm. Analysis 031- t oxyl (W cm) enoxy) 0 culated for C1sH22O2C14t 36.54% Cl; found Examples of other aliphatic groups in the alkyl ether linkage in the general formula are: methyl, n-propyl, isopropyl, isobutyl, sec-butyl, n-amyl, isoamyl, 2-methyl butyl, heptyl, lauryl, hydroxyethyl, and ethers thereof, fl-bromoethyl, a-ChlO- ropropyl, p-eyanothyl. Examples of other aromatic groups in the aryl ether linkage in the general formula are shown in the following further compounds illustrative of the present invention:

1 ,6 cyanoethoxy-l-p-ch1orophenoxy-2,2,2- trichloroethane,

1 a. chloropropoxy l (2,4-5-trichlorophenoxy) -2,2,2-trichloroethane,

1 cyclohexyloxy l-(p-tert.-butylphenoxy)- 2,2,2-trichloroethane,

Example 13 Leaves of the broad bean (Vicia faba) infested with pea aphids (Macrosiphu-m pisi) were sprayed with 1% aqueous emulsions of various mixed aliphatic-aromatic acetals of chloral, the emulsions containing a small amount of 'a commercial wetting agent which was known to be non-toxic to the organisms under test. There were variable numbers of'insects in four replicates of each treatment. Observations were made after 24 hours to disclose the kill of aphids. The percent mortality and the number of pea aphids on the leaves treated with the various mixed aliphatic-aromatic acetals of chloral are shown in the following table. In untreated (check) leaves infested with 361 aphids, the mortality was 1.8%.

No. of Per Cent Che/1181 Aphids Mortality l-Ethoxy-1-phenoxy-2,2,Z-trichloroethane.- 211 96. 7 l-Ethoxy 1 (p chlorophenoxy) 2,2,2 trichloroethan v 140 95. 0 l-Ethoxy-l-(o-chlorophenoxy)-2,2,2-trichloroethane 233 90. l l-Ethoxy-l-(m-chlorophenoxy)-2 2,2-trichloroethane 211 94. 3 l-Ethoxy-l-(2,4-dich1orophenoxy5-2,2,2 trichloroethane 173 80. 9 l-Ethoxy'l-(2,4,6-trichlorophenoxy)-2,2,2-tricblorocthane- 2,01 86. l l-Ethoxy-l-(2,4,5-trichlorophenoxy)-2,2,2-trichloroethane 198 62. l l-E thoxy-l-(p-nitrophenoxy)-2,2,2trichloroethane 216 28. 2 1-But0xy-1-(p-chlorophenoxy)-2,2,2-trichlor0ethane 199 89. 4 l-HexoXy-l-(p-chlorophenoxy)-2,2,2-trichloroethane. 211 97. 6 l-Octoxy-lp-chloro henoxy)-2,2,2-trichloroethane 153 92. 8 l-fl-chloroet oxy-l-p enoxy-2.2,2-trichlorocthane 224 63. 8 l-B-chloroethoxy-l-(p-chlorophenoxy)-2,2,2-trichloroethane. v 185 86. 5 l-fl-chloroethoxy-l-(2,4-dich1orophenoxy)-2 2,2-trichloroethane 166 83. l 1-fi-chloroethoxy-1-(2-naphthoxy)-2,2,2-tr chloroethane 201 84. 6 l-Ethoxy-l-(p-methylphenoxy)-2,2,2-trichloroethane. 133 86. 5 l-Ethoxy-l-(p-ethoxyphenoxy)-2,2,2trichloroethane 186 91. 4

1 isobutyloxy 1-(p-tert.-butylphenoxy)- 2,2,2-trichloroethane.

The following examples illustrate the effectiveness of various mixed aliphatic-aromatic acetals of chloral as insecticides:

Example A Pinto bean leaves were sprayed with 1% aqueous emulsions of various mixed aliphatic-are matic acetals of chloral, the emulsions containing a small amount of a commercial dispersing agent which was known to be non-toxic to the Example C.

Pinto bean leaves infested with red spider mites (Tetranychus telarius) were sprayed with 1% emulsions of various mixed aliphatic-aromatic acetals of chloral, the emulsions containing a small amount of wetting agent known to be nontoxic to the organisms under test. There were variable numbers of mites in four replicates of each treatment. Observations were made after 24 hours to disclose the kill of mites. The per- 75 cent mortality and number of mites on the leaves treated with the various mixed aliphatic-aromatic acetals of chloral are shown in the table below. In untreated (check) leaves infested with 288 red spider mites, the mortality was 5.9% after 24 8 in which X is a radical selected from the group consisting of alkyl, cycloalkyl, haloalkyl, cyanoalkyl, alkoxyalkyl and hydroxvallqll radicals having up to 12 carbon atoms and Y is a radical sehours. lected from the group consisting of phenyl, naph- N o. of Per Cent Chem! Mites Mortality 1-Ethoxy-l-phenoxy-2,2,Z-trichloroethanc. 241 100. 0 i-Ethoxy-l-(p-chlorophenoxy)-2,2,2-trichloroethane 179 99. 4 l-E thoxy-l-(o-chlorophenoxy)-2,2,2-trichloroethane 189 100. 0 l-Ethoxy-l-(m-cl1lorophenoxy)-2,2,2-trichloroethane 263 100. 0 l-Ethoxy-l-(2,4-dicblorophenoxy)-2,2,2-tricl]loroethane 139 100. 0 i-Ethoxy-l-(2,4,B-tricblcrophenoxy)-2,2,2-trlchloroethane. 163 99. 4 l-Ethoxy-l-(2,4,5-trichlorophenoxy)-2,2,2-trlcbloroethane 148 80. 4 1-Ethoxy-l-(p-nitrophenoxy)-2,2,2-trichloroethane 88 14. 8 l-B utoxy-l-(p-chlorophenoxy)-2,2,2-trichioroethape"--- 196 100. 0 l-Hexoxy-l-(pchlorophenoxy)-2,2,2-tr1chloroethane 158 100.0 l-Octoxy-l-(p'chlorcheuoxy) -2,2,2-trichloroethane 152 12. 3 l-B-chloroethoxy-l-p epoxy-2,2.2-trichioroethane 253 96. 4 ldchloroethoxy-l-(p-chlorophenoxy)-2,2,2-trichloroethane- 193 36. 3 1-fi-chloroethoxy-l-(2,4-dichiorophenoxy)-2.2,2-trichloroethane. 177 22. 0 l-,B-chloroetboxy-l-(2-r1aphthoxy)-2,2,2-trichloroethane 191 S1. 7 1-Ethoxy-1-(p-methylpbenoxy)-2,2,2-tricbloroethane 123 100. 0 l-Ethoxy-l-(pethoxyphenoxy)-2,2,2-trichloroethane 149 100. 0

and alkoxyphenyl radicals having 6 to 10 carbon atoms, and'a carrier therefor.

2. An insecticidal composition comprising as an active ingredient a l-alkoxy-l-chlorcphenoxy- 2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms, and a carrier therefor.

3. A compound having the general formula in which X is a radical selected from the group consisting of alkyl, cycloalkyl, haloalkyl, cyanoalkyl, alkoxyalkyl and hydroxyalkyl radicals having up to 12 carbon atoms and Y is a radical selected from the group consisting of phenyl, naphthyl, halophenyl, nitrophenyl, allgvlphenyl, and alkoxyphenyl radicals having 6 to 10 carbon atoms.

4. A l-allroxy-1-aryloxy-2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms and the aryloxy group has 6 to 10 carbon atoms.

5. A l-alkoxy-1-chlorophenoxy-2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms.

6. l-ethoxy 1 (p-chlorophenoxy)-2,2,2-trichloroethane.

7. l-ethoxy-l- (2,4 -dichlorophenoxy) -2,2,2-trichloroethane.

8. An insecticidal composition comprising as an active ingredient a compound having the general formula thyl, halophenyl, nitrophenyl, alkylphenyl, and alkoxyphenyl radicals having 6 to 10 carbon atoms, and a liquid carrier therefor.

9. An insecticidal composition comprising as an active ingredient a 1-alkoxy-l-chlorophencxy- 2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms, and a liquid carrier therefor.

10. An insecticidal composition comprising as an active ingredient a compound having the general formula in which X is a radical selected from the group consisting of alkyl, cycloalkyl, haloalkyl, cyanoalkyl, alkoxyallevl and hydroxyalkyl radicals having up to 12 carbon atoms and Y is a radical selected from the group consisting of phenyl, naphthyl, halophenyl, nitrophenyl, alkylphenyl, and alkoxyphenyl radicals having 6 to 10 carbon atoms, and a powdered solid carrier therefor.

11. An insecticidal composition comprising as an active ingredient a l-alkoxy-l-chlorophenoxy- 2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms, and a powdered solid carrier therefor.

12. An insecticidal composition comprising an aqueous emulsion of a compound having the general formula or ole-on c1 in which X is a radical selected from the group consisting of alkyl, cycloalkyl, haloalkyl, cyanoalkyl, alkoxyalkyl and hydroxyalkyl radicals having up to 12 carbon atoms and Y is a radical selected from the group consisting of phenyl, naphthyl, halophenyl, nitrophenyl, alkylphenyl, and alkoxyphenyl radicals having 6 to 10 carbon atoms, said aqueous emulsion containing a dispersing agent.

13. An insecticidal composition comprising an aqueous emulsion of a l-alkoxy-l-chlorophenoxy- 2,2,2-trichloroethane in which the alkoxy group has up to 12 carbon atoms, said aqueous emulsion containing a dispersing agent.

14. An insecticidal composition comprising l-ethoxy-l-(p-chlorophenoxy) 2,2,2 trichloro- REFERENCES CITED ethane, and a carrier therefor. The H i 15. An insecticidal composition comprising me of ggggfi are in the l-ethoxy-l-(p-chlorophenoxy) 2,2,2 trichloroethane, and a liquid carrier therefor. 5 UNITED STATES PATENTS 16. An insecticidal composition comprising Number Name Date l-ethoxy 1 (p-chlorophenoxy) -2,2,2-tr1ch10r0- 2,329,074 Muller Sept. 7, 1943 ethane, and a powdered solid carrier therefor.

17. An insecticidal composition comprising OTHER REFERENCES an aqueous emulsion of l-ethoxy-l-(p-chloro- 10 "Science News Letter, D- 8 phenoxy) -2,2,2-trichloroethane, said aqueous DY in Scientific a y.) emulsion containing a dispersing agent. Fieser et 111., Organic Chemistry, p. 32 (1944),

Heath 8: Co., publishers, Boston. (Copy in Div. 6.) WALTER, 1 Oddo et al., Gazz. Chim. Ital, vol. 36, sec. 1,

THEODORE W. KERR. I5 DD. 488, 489. (Copy in Scientific Library.) 

1. AN INSECTICIDAL COMPOSITION COMPRISING AS AN ACTIVE INGREDIENT A COMPOUND HAVING THE GENERAL FORMULA 